By‐Product‐Free Siloxane‐Bond Formation and Programmed One‐Pot Oligosiloxane Synthesis. Issue 12 (2nd February 2017)

• Record Type: Journal Article
• Authors: Matsumoto, Kazuhiro; Sajna, Kappam Veettil; Satoh, Yasushi; Sato, Kazuhiko; Shimada, Shigeru
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 12(2017)
• Page Start: 3168
• Page End: 3171
• Publication Date: 2017-02-02
• Subjects: boron catalysis -- hydrosilylation -- rearrangement -- silanes -- siloxanes; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201611623
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Siloxane bonds are usually synthesized by condensation reactions, such as hydrolysis/dehydration and cross‐coupling reactions, in which the generation of by‐products during bond formation can not be avoided. We have developed a one‐pot sequence of iridium‐catalyzed silyl ester hydrosilylation and boron‐catalyzed rearrangement of the resulting disilyl acetals for the construction of siloxane bonds, in principle without the formation of any by‐products. Moreover, the programmed synthesis of tri‐, tetra‐, and pentasiloxanes was possible in a single flask by combining the above sequence of iridium‐catalyzed hydrosilylation and boron‐catalyzed rearrangement with a boron‐catalyzed cross‐coupling reaction. The obtained oligosiloxanes are difficult to synthesize selectively by other known synthetic procedures. Abstract : All in one and one for all : A one‐pot sequence involving the iridium‐catalyzed hydrosilylation of silyl esters and boron‐catalyzed rearrangement enabled by‐product‐free siloxane‐bond formation. Oligosiloxanes could also be synthesized in a single flask in a programmed fashion by a sequence of iridium‐catalyzed hydrosilylation, boron‐catalyzed rearrangement, and boron‐catalyzed cross‐coupling (see scheme).